ES2216863T3 - RIGID FOAMS OF FINE ALVEOL POLYURETHANE EXPANDED WITH WATER. - Google Patents

RIGID FOAMS OF FINE ALVEOL POLYURETHANE EXPANDED WITH WATER.

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Publication number
ES2216863T3
ES2216863T3 ES00906260T ES00906260T ES2216863T3 ES 2216863 T3 ES2216863 T3 ES 2216863T3 ES 00906260 T ES00906260 T ES 00906260T ES 00906260 T ES00906260 T ES 00906260T ES 2216863 T3 ES2216863 T3 ES 2216863T3
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polyol
water
mol
average molecular
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Torsten Heinemann
Walter Klan
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Covestro Deutschland AG
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Bayer MaterialScience AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Materials For Medical Uses (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Thermal Insulation (AREA)

Abstract

Procedimiento para la fabricación de espumas rígidas de poliuretano y/o de poliisocianurato de alvéolos finos por transformación de A) un poliisocianato con un contenido en NCO del 20 al 48% en peso con B) un componente de poliol presente en forma de emulsión, que presenta como media al menos dos grupos reactivos frente a isocianato y que contiene 1) a) al menos un poliol al menos difuncional inmiscible con agua, con un peso molecular medio en número de 150 a 12.500 g/mol, b) al menos un polioléster o polioleteréster con un peso molecular medio en número de 100 a 30.000 g/mol, 2) agua, 3) catalizador, 4) dado el caso coadyuvantes y aditivos.Process for the manufacture of rigid foams of polyurethane and / or polyisocyanurate of fine alveoli by transformation of A) a polyisocyanate with an NCO content of 20 to 48% by weight with B) a polyol component present in the form of an emulsion, which It has at least two isocyanate reactive groups and containing 1) a) at least one at least one water-immiscible polyol, with a number average molecular weight of 150 to 12,500 g / mol, b) at least one polyol ester or polyolether with a number average molecular weight of 100 to 30,000 g / mol, 2) water, 3) catalyst, 4) if necessary adjuvants and additives.

Description

Espumas rígidas de poliuretano de alvéolos finos expandidas con agua.Rigid foamed polyurethane foams expanded with water.

La invención trata de un procedimiento para la fabricación de espumas rígidas de alvéolos finos, expandidas con agua, que presentan grupos uretano y/o isocianurato, mediante la transformación de poliisocianatos con un componente de poliol presente en forma de emulsión. La invención trata además de espumas de poliuretano de alvéolos abiertos que se pueden espumar en molde.The invention deals with a method for manufacture of rigid foams of fine alveoli, expanded with water, which have urethane and / or isocyanurate groups, by means of transformation of polyisocyanates with a polyol component present in the form of emulsion. The invention also deals with foams polyurethane in open cells that can be foamed in mold.

Según el estado de la técnica, las espumas rígidas de poliuretano se fabrican a partir de polioles con como media al menos tres grupos hidroxilo por molécula, isocianatos al menos difuncionales, catalizadores, agentes de expansión y copolímeros de bloques de polisiloxano/polioxialquileno, así como dado el caso de aditivos habituales.According to the state of the art, the foams rigid polyurethane are manufactured from polyols with as average at least three hydroxyl groups per molecule, isocyanates at less difunctional, catalysts, expansion agents and polysiloxane / polyoxyalkylene block copolymers, as well as in the case of habitual additives.

En G. Oertel (ed.): "Kunststoffhandbuch", volumen VII, C. Hanser Verlag, Munich, 1983, en Houben-Weyl: "Methoden der organischen Chemie", volumen E20, Thieme Verlag, Stuttgart 1987, pág. 1561 a 1757, y en "Ullmann's Encyclopedia of Industrial Chemistry", vol. A21, VCH, Weinheim, 4ª edición 1992, pág. 665 a 715, se encuentra un resumen del estado de la técnica, de las materias primas usadas y de los procedimientos aplicables.In G. Oertel (ed.): "Kunststoffhandbuch", Volume VII, C. Hanser Verlag, Munich, 1983, in Houben-Weyl: "Methoden der organischen Chemie", Volume E20, Thieme Verlag, Stuttgart 1987, p. 1561 to 1757, and in "Ullmann's Encyclopedia of Industrial Chemistry", vol. A21, VCH, Weinheim, 4th edition 1992, p. 665 to 715, there is a summary of the state of the art, of the raw materials used and of the applicable procedures.

En general se usan polioléteres o poliolésteres o mezclas de ellos, estando presentes en la mezcla de polioles usada como media al menos tres grupos hidroxilo por molécula y encontrándose el índice de hidroxilo de la mezcla de polioles usada entre 100 y 900.In general, polyethers or polyesters are used or mixtures thereof, being present in the mixture of polyols used on average at least three hydroxyl groups per molecule and meeting the hydroxyl index of the polyol mixture used between 100 and 900.

Normalmente, las espumas rígidas de poliuretano generadas son predominantemente de alvéolos cerrados. Su peso específico asciende a entre 5 y 950 kg\cdotm^{-3}, normalmente a entre 10 y 350 kg\cdotm^{-3}, usándose con especial frecuencia pesos específicos de 20 a 70 kg\cdotm^{-3}.Normally, rigid polyurethane foams generated are predominantly of closed alveoli. His weight specific amounts to between 5 and 950 kg · 3, usually between 10 and 350 kg • 3, being used with special frequency specific weights of 20 to 70 kg • 3.

Los desarrollos más recientes en el campo de las espumas rígidas de poliuretano se dirigen a la fabricación selectiva de espumas rígidas de poliuretano de alvéolos en gran parte abiertos, modificadas con poliuretano o poliisocianurato, que se usan como materiales aislantes en, por ejemplo, paneles aislantes por vacío. Para el uso de las espumas rígidas mencionadas de alvéolos abiertos en paneles aislantes por vacío es especialmente importante que el diámetro alveolar sea lo más pequeño posible, puesto que esto determina la eficacia del aislamiento. Cuanto menor sea el diámetro alveolar, tanto menos hay que evacuar para lograr un efecto aislante definido. El diámetro alveolar medio de las espumas rígidas de poliuretano expandidas con agua, obtenidas según los procedimientos del estado de la técnica es habitualmente superior a 150 \mum; las espumas con este diámetro alveolar habitualmente no son adecuadas para aplicaciones de vacío.The most recent developments in the field of rigid polyurethane foams are directed to selective manufacturing of rigid polyurethane foams of alveoli largely open, modified with polyurethane or polyisocyanurate, which use as insulating materials in, for example, insulating panels by vacuum For the use of the mentioned rigid foams of open cells in vacuum insulating panels is especially important that the alveolar diameter be as small as possible, since this determines the effectiveness of the insulation. The smaller be the alveolar diameter, the less you have to evacuate to achieve a definite insulating effect. The average alveolar diameter of the foams rigid polyurethane expanded with water, obtained according to prior art procedures is usually superior to 150 µm; foams with this alveolar diameter usually do not They are suitable for vacuum applications.

La fabricación de espumas rígidas de poliuretano de alvéolos abiertos es conocida en principio. Así, el documento US-A 5350777 describe el uso de sales alcalinotérreas de ácidos grasos de cadena larga como abridores de alvéolos.The manufacture of rigid polyurethane foams Open socket is known in principle. So, the document US-A 5350777 describes the use of salts alkaline earth long-chain fatty acids as openers for alveoli

En el documento EP-A 498628 consta la fabricación de espumas rígidas de alvéolos abiertos mediante la acción de un agente de expansión termoactivado. Este procedimiento presenta el inconveniente de que los alvéolos de la espuma únicamente se pueden abrir allí donde se supere una temperatura mínima en el transcurso del proceso de espumación, de manera que las espumas obtenidas no presentan una proporción de alvéolos abiertos uniformemente alta en todo el volumen relleno de espuma.In document EP-A 498628 It consists of the manufacture of rigid foams of open cells by the action of a thermo-activated expansion agent. East procedure has the disadvantage that the alveoli of the foam can only be opened where it exceeds one minimum temperature during the foaming process, of so that the foams obtained do not have a proportion of open sockets uniformly high throughout the volume filled with foam.

En el documento DE-A 4303809 se da a conocer un procedimiento para la fabricación de espumas rígidas con una mayor proporción de alvéolos abiertos, en el que se usa el efecto abridor de alvéolos de un aditivo de poliolefina líquido. Este procedimiento posee el inconveniente de un estrecho espectro de aplicación y el inconveniente adicional de que a una mayor dosificación del aditivo de poliolefina se produce rápidamente la formación de alvéolos más gruesos.In document DE-A 4303809, discloses a procedure for the manufacture of rigid foams with a greater proportion of open alveoli, in which the socket opening effect of a liquid polyolefin additive. This procedure has the disadvantage of a narrow spectrum of application and the additional inconvenience that at a higher Dosage of the polyolefin additive quickly occurs the formation of thicker alveoli.

En los documentos US-A 5250579 y US-A 5312846 se da a conocer el efecto abridor de alvéolos de sustancias con una tensión superficial inferior a 23 mJ\cdotm^{-2}. Éstas presentan el inconveniente de que contienen halógeno fijado de forma orgánica. El documento GB-A-2324789 da a conocer espumas de poliuretano de alvéolos abiertos. A la mezcla de reacción se añade un compuesto de flúor insoluble en forma de emulsión.In documents US-A 5250579 and US-A 5312846 discloses the opening effect of alveoli of substances with a surface tension less than 23 mJ • -2. These have the disadvantage that they contain organically fixed halogen. The document GB-A-2324789 discloses foams of open socket polyurethane. To the reaction mixture is added an insoluble fluorine compound in the form of an emulsion.

El objetivo de la presente invención era encontrar un procedimiento para la fabricación de espumas rígidas de poliuretano de alvéolos finos y, dado el caso, de alvéolos abiertos, expandidas con agua, en el que las espumas de poliuretano de acuerdo con la invención conservaran las propiedades finales deseadas - alvéolos abiertos y alvéolos finos - también en el caso de una espumación en molde.The objective of the present invention was find a procedure for the manufacture of rigid foams of polyurethane of fine alveoli and, if necessary, of open alveoli, expanded with water, in which polyurethane foams agree with the invention they will retain the desired final properties - open alveoli and fine alveoli - also in the case of a mold foaming.

Ahora se descubrió que cuando se espuma un poliisocianato con una formulación de poliol que contiene agua y que está presente en forma de emulsión se obtienen espumas rígidas de poliuretano de alvéolos finos y, dado el caso, de alvéolos abiertos.Now it was discovered that when you foam a polyisocyanate with a polyol formulation that contains water and that is present in the form of an emulsion rigid foams of polyurethane of fine alveoli and, where appropriate, of alveoli open.

El objeto de la invención es, por lo tanto, un procedimiento para la fabricación de espumas rígidas de poliuretano y/o de poliisocianurato de alvéolos finos mediante la transformación deThe object of the invention is therefore a procedure for the manufacture of rigid polyurethane foams and / or fine alveoli polyisocyanurate by transformation from

A) un poliisocianato con un contenido en NCO del 20 al 48% en peso conA) a polyisocyanate with an NCO content of 20 to 48% by weight with

B) un componente de poliol presente en forma de emulsión, que presenta como media al menos dos grupos reactivos frente a isocianato y que contieneB) a polyol component present in the form of emulsion, which has at least two reactive groups on average against isocyanate and containing

1) a) al menos un poliol al menos difuncional inmiscible con agua, con un peso molecular medio en número de 150 a 12.500 g/mol,1) a) at least one at least difunctional polyol immiscible with water, with a number average molecular weight of 150 to 12,500 g / mol,

1) b) al menos un polioléster o polioleteréster con un peso molecular medio en número de 100 a 30.000 g/mol,1) b) at least one polyol or polyoleter with a number average molecular weight of 100 to 30,000 g / mol,

2) agua,2) water,

3) catalizador,3) catalyst,

4) dado el caso coadyuvantes y aditivos.4) if necessary adjuvants and additives.

El objeto de la invención es asimismo una espuma de moldeo de poliuretano o de poliisocianurato con una proporción de alvéolos abiertos >85%, preferentemente >90%, medida según DIN ISO4590-92, siendo el grado de compactación >3% respecto al volumen mínimo de relleno. Esta espuma se puede fabricar mediante el procedimiento de acuerdo con la invención.The object of the invention is also a foam molding of polyurethane or polyisocyanurate with a proportion of open cells> 85%, preferably> 90%, measured according to DIN ISO4590-92, the degree of compaction being> 3% regarding the minimum filling volume. This foam can be manufactured by the method according to the invention.

Las formulaciones de poliol de acuerdo con la invención contienen al menos un poliol al menos difuncional inmiscible con agua, es decir, con al menos dos grupos funcionales reactivos frente a isocianato que presentan átomos de hidrógeno, con un peso molecular medio en número de 150 a 12.500 g/mol, preferentemente de 200 a 1.500 g/mol. Ejemplos de ellos son triglicéridos, por ejemplo aceite de ricino o aceite de ricino modificado por reacciones de transesterificación/amidación con alcoholes o aminas mono- o polifuncionales, o ácidos grasos, tales como ácido esteárico, ácido oleico, ácido linoleico o ácido ricinoleico. La formulación de poliol contiene de 5 a 99 partes en peso, preferentemente de 20 a 80 partes en peso, de este componente.Polyol formulations according to the invention contain at least one at least difunctional polyol immiscible with water, that is, with at least two functional groups isocyanate reagents that have hydrogen atoms, with a number average molecular weight of 150 to 12,500 g / mol, preferably from 200 to 1,500 g / mol. Examples of them are triglycerides, for example castor oil or castor oil modified by transesterification / amidation reactions with mono- or polyfunctional alcohols or amines, or fatty acids, such as stearic acid, oleic acid, linoleic acid or acid ricinoleic. The polyol formulation contains 5 to 99 parts in weight, preferably 20 to 80 parts by weight, of this component.

Para lograr la funcionalidad necesaria para la espumación, las formulaciones de poliol de acuerdo con la invención contienen al menos un poliol que presenta al menos dos átomos de hidrógeno reactivos frente a isocianatos y un peso molecular medio en número de 150 a 12.500 g/mol, preferentemente de 200 a 1.500 g/mol. Estos polioles se pueden obtener por poliadición de óxidos de alquileno, como, por ejemplo, óxido de etileno, óxido de propileno, óxido de butileno, óxido de dodecilo u óxido de estireno, preferentemente óxido de propileno u óxido de etileno, a compuestos iniciadores, tales como agua o alcoholes polifuncionales, tales como sacarosa, sorbitol, pentaeritrita, trimetilolpropano, glicerina, propilenglicol, etilenglicol, dietilenglicol, así como mezclas de los compuestos iniciadores mencionados. Como compuestos iniciadores también se pueden usar amoniaco o compuestos que presentan al menos un grupo amino primario, secundario o terciario, por ejemplo aminas alifáticas, tales como etilendiamina, oligómeros de la etilendiamina (por ejemplo, dietilentriamina, trietilentetramina o pentaetilenhexamina), etanolamina, dietanolamina, trietanolamina, N-metil- o N-etildietanolamina, 1,3-propilendiamina, 1,3- o 1,4-butilendiamina, 1,2-hexametilendiamina, 1,3-hexametilendiamina, 1,4-hexametilendiamina, 1,5-hexametilendiamina o 1,6-hexametilendiamina, aminas aromáticas, tales como fenilendiaminas, toluilendiaminas (2,3-toluilendiamina, 3,4-toluilendiamina, 2,4-toluilendiamina, 2,5-toluilendiamina, 2,6-toluilendiamina o mezclas de los isómeros mencionados), 2,2'-diaminodifenilmetano, 2,4'-diaminodifenilmetano, 4,4'-diaminodifenilmetano o mezclas de estos isómeros. La formulación de poliol contiene de 0 a 95 partes en peso, preferentemente de 10 a 40 partes en peso, de este componente.To achieve the necessary functionality for the foaming, polyol formulations according to the invention they contain at least one polyol that has at least two atoms of hydrogen reactants against isocyanates and an average molecular weight in number from 150 to 12,500 g / mol, preferably from 200 to 1,500 g / mol These polyols can be obtained by polyaddition of oxides of alkylene, such as ethylene oxide, propylene oxide, butylene oxide, dodecyl oxide or styrene oxide, preferably propylene oxide or ethylene oxide, to compounds initiators, such as water or polyfunctional alcohols, such as sucrose, sorbitol, pentaerythrite, trimethylolpropane, glycerin, propylene glycol, ethylene glycol, diethylene glycol, as well as mixtures of the starting compounds mentioned. As starter compounds Ammonia or compounds that have at least one can also be used a primary, secondary or tertiary amino group, for example amines aliphatic, such as ethylenediamine, oligomers of ethylenediamine (for example, diethylenetriamine, triethylenetetramine or pentaethylenehexamine), ethanolamine, diethanolamine, triethanolamine, N-methyl- or N-ethyldiethanolamine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-hexamethylene diamine, 1,3-hexamethylene diamine, 1,4-hexamethylene diamine, 1,5-hexamethylene diamine or 1,6-hexamethylene diamine, aromatic amines, such such as phenylenediamines, toluylenediamines (2,3-toluylenediamine, 3,4-toluylenediamine, 2,4-toluylenediamine, 2,5-toluylenediamine, 2,6-toluylenediamine or mixtures of the isomers mentioned), 2,2'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane or mixtures thereof isomers The polyol formulation contains 0 to 95 parts in weight, preferably 10 to 40 parts by weight, of this component.

Las formulaciones de poliol de acuerdo con la invención contienen también poliolésteres o polioleterésteres con un peso molecular medio en número de 100 a 30.000 g/mol, preferentemente de 150 a 10.000 g/mol, muy preferentemente de 200 a 600 g/mol. Los poliolésteres se pueden fabricar a partir de ácidos dicarboxílicos aromáticos y/o alifáticos y polioles que presentan al menos dos grupos hidroxilo. Ejemplos de ácidos dicarboxílicos son ácido ftálico, ácido fumárico, ácido maleico, ácido aceláico, ácido glutárico, ácido adípico, ácido subérico, ácido tereftálico, ácido isoftálico, ácido decanodicarboxílico, ácido malónico, ácido glutárico y ácido succínico. Se pueden usar ácidos dicarboxílicos individuales, así como cualquier mezcla de diferentes ácidos dicarboxílicos. En lugar de los ácidos dicarboxílicos libres también se pueden usar los derivados correspondientes de los ácidos dicarboxílicos, como, por ejemplo, mono- o diésteres de ácido dicarboxílico de alcoholes con uno a cuatro átomos de carbono, o anhídridos de ácido dicarboxílico. Como componente alcohólico para la esterificación se usan preferentemente: Etilenglicol, dietilenglicol, trietilenglicol, tetraetilenglicol, 1,2-propanodiol, 1,3-propanodiol, 1,4-butanodiol, 1,5-pentanodiol, 1,5-hexanodiol, 1,10-decanodiol, glicerina, trimetilolpropano o sus mezclas. Las formulaciones de poliol de acuerdo con la invención también pueden contener polieterésteres, como los que se pueden obtener, por ejemplo, según el documento EP-A 250967 por reacción de anhídrido del ácido ftálico con dietilenglicol y, seguidamente, con óxido de etileno. La formulación de poliol contiene hasta 90, preferentemente de 5 a 30, partes en peso de polioléster.Polyol formulations according to the invention also contain polyesters or polyoletersters with a number average molecular weight of 100 to 30,000 g / mol, preferably from 150 to 10,000 g / mol, most preferably from 200 to 600 g / mol Polyesters can be manufactured from acids aromatic and / or aliphatic dicarboxylics and polyols presenting the minus two hydroxyl groups. Examples of dicarboxylic acids are phthalic acid, fumaric acid, maleic acid, acetic acid, acid glutaric acid, adipic acid, subic acid, terephthalic acid, acid isophthalic, decanedicarboxylic acid, malonic acid, acid Glutaric and succinic acid. Dicarboxylic acids can be used individual as well as any mixture of different acids dicarboxylic. Instead of free dicarboxylic acids too corresponding derivatives of acids can be used dicarboxylic acids, such as, for example, mono- or diesters of acid dicarboxylic alcohol with one to four carbon atoms, or dicarboxylic acid anhydrides. As an alcoholic component for The esterification is preferably used: Ethylene Glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,10-decanediol, glycerin, trimethylolpropane or mixtures thereof. The formulations of polyol according to the invention may also contain polyethers, such as those obtainable, for example, according to EP-A 250967 for anhydride reaction of phthalic acid with diethylene glycol and then with oxide of ethylene. The polyol formulation contains up to 90, preferably 5 to 30, parts by weight of polyester.

Las formulaciones de poliol de acuerdo con la invención contienen también al menos un catalizador en cantidades de 0 a 10 partes en peso, preferentemente de 0,5 a 5 partes en peso. De acuerdo con la invención se pueden usar los catalizadores habituales en la química del poliuretano. Ejemplos de este tipo de catalizadores son: Trietilendiamina, N,N-dimetilciclohexilamina, tetrametilendiamina, 1-metil-4-dimetil-aminoetilpiperazina, trietilamina, tributilamina, dimetilbencilamina, N,N',N''tris-(dimetilaminopropil)-hexahidrotriazina, dimetilaminopropilformamida, N,N,N',N'-tetrametiletilendiamina, N,N,N',N'-tetrametilbutanodiamina, tetrametilhexanodiamina, pentametildietilentriamina, tetrametildiaminoetil éter, dimetilpiperazina, 1,2-dimetilimidazol, 1-azabiciclo[3,3,0]octano, bis-(dimetilaminopropil)-
urea, N-metilmorfolina, N-etilmorfolina, N-ciclohexilmorfolina, 2,3-dimetil-3,4,5,6-tetrahidropirimidina, trietanolamina, dietanolamina, triisopropanolamina, N-metildietanolamina, N-etildietanolamina, dimetiletanolamina, acetato de estaño(II), octoato de estaño(II), etilhexoato de estaño(II), laurato de estaño(II), diacetato de dibutilesaño, dilaurato de dibutilestaño, maleato de dibutilestaño, diacetato de dioctilestaño, tris-(N,N-dimetilaminopropil)-s-hexahidrotriazina, hidróxido de tetrametilamonio, acetato de potasio, acetato de sodio, hidróxido de sodio o mezclas de estos u otros catalizadores similares.The polyol formulations according to the invention also contain at least one catalyst in amounts of 0 to 10 parts by weight, preferably 0.5 to 5 parts by weight. In accordance with the invention, the catalysts customary in polyurethane chemistry can be used. Examples of this type of catalysts are: Triethylenediamine, N, N-dimethylcyclohexylamine, tetramethylenediamine, 1-methyl-4-dimethyl-aminoethylpiperazine, triethylamine, tributylamine, dimethylbenzylamine, N, N ', N''tris- (dimethylaminopropyl) -hexa dimethylaminopropylformamide, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, tetramethylhexanodiamine, pentamethyldiethylenetriamine, tetramethyldiaminoethyl ether, dimethylpiperazine, 1,2-dimethylimidazole [3,3 -,0 ] octane, bis- (dimethylaminopropyl) -
urea, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, triethanolamine, diethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, dimethylethanolamine, tin acetate ( II), tin octoate (II), tin ethylhexoate (II), tin laurate (II), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, tris- (N, N-dimethylaminopropyl) - s-hexahydrotriazine, tetramethylammonium hydroxide, potassium acetate, sodium acetate, sodium hydroxide or mixtures of these or other similar catalysts.

De acuerdo con la invención se pueden coutilizar también emulsionantes iónicos y no iónicos en cantidades de 0 a 10 partes en peso, preferentemente de 0,5 a 2 partes en peso. Estos emulsionantes se describen, por ejemplo, en "Römpp Chemie Lexikon", volumen 2, Thieme Verlag Stuttgart, 9ª edición 1991, pág. 1156 en adelante.According to the invention they can be used also ionic and non-ionic emulsifiers in amounts from 0 to 10 parts by weight, preferably 0.5 to 2 parts by weight. These Emulsifiers are described, for example, in "Römpp Chemie Lexikon ", volume 2, Thieme Verlag Stuttgart, 9th edition 1991, P. 1156 onwards.

El componente de poliol de acuerdo con la invención contiene de 0,1 a 10 partes en peso, preferentemente de 0,5 a 5 partes en peso, de agua.The polyol component according to the invention contains from 0.1 to 10 parts by weight, preferably of 0.5 to 5 parts by weight of water.

Para el procedimiento de acuerdo con la invención es esencial que el componente de poliol se use en forma de emulsión. Esto significa que al menos uno de los constituyentes del componente de poliol debe ser inmiscible con los demás constituyentes, es decir en general que está contenido al menos un compuesto insoluble en agua o inmiscible con agua que presenta átomos de hidrógeno reactivos frente a isocianato. Se ha demostrado que el uso de un componente de poliol presente en forma de emulsión produce espumas de alvéolos bastante más finos.For the process according to the invention It is essential that the polyol component be used in the form of an emulsion. This means that at least one of the constituents of the component Polyol must be immiscible with the other constituents, that is in general that at least one insoluble compound is contained in water or immiscible with water that has hydrogen atoms isocyanate reagents. It has been shown that the use of a Polyol component present in the form of emulsion produces foams of thinner alveoli.

Como componente de isocianato se pueden usar poliisocianatos aromáticos, como los que se describen en Justus Liebigs Annalen der Chemie, 562 (1949) 75, por ejemplo aquellos de fórmulaAs the isocyanate component, aromatic polyisocyanates can be used, such as those described in Justus Liebigs Annalen der Chemie, 562 (1949) 75, for example those of formula

Q(NCO)_{n},Q (NCO) n,

en la quein the what

nn
puede adoptar valores de 2 a 4, preferentemente 2, ycan adopt values from 2 to 4, preferably 2, and

QQ
significa un resto hidrocarbonado alifático con 2 a 18, preferentemente 6 a 10 átomos de C, un resto hidrocarbonado cicloalifático con 4 a 15, preferentemente 5 a 10 átomos de C, un resto hidrocarbonado aromático con 8 a 15, preferentemente 8 a 13 átomos de C.means a rest aliphatic hydrocarbon with 2 to 18, preferably 6 to 10 atoms of C, a cycloaliphatic hydrocarbon moiety with 4 to 15, preferably 5 to 10 C atoms, a hydrocarbon moiety aromatic with 8 to 15, preferably 8 to 13 C atoms.

Se prefieren los poliisocianatos que se describen en el documento DE-OS 2832253. En general se usan muy preferentemente los poliisocianatos fácilmente accesibles técnicamente, por ejemplo el 2,4- y 2,6-toluilendiisocianato, así como cualquier mezcla de estos isómeros ("TDI"), polifenilpolimetilenpoliisocianatos, como los que se fabrican por condensación de anilina/formaldehído y fosgenación siguiente ("MDI bruto"), y poliisocianatos que presentan grupos carbodiimido, grupos uretano, grupos alofanato, grupos isocianurato, grupos urea o grupos biuret ("poliisocianatos modificados"), en especial los poliisocianatos modificados que derivan del 2,4- y 2,6-toluilendiisocianato o del 4,4'- y/o 2,4'-difenilmetanodiisocianato.The polyisocyanates described are preferred. in DE-OS 2832253. In general they are used very preferably easily accessible polyisocyanates technically, for example 2,4- and 2,6-toluylenediisocyanate, as well as any mixture of these isomers ("TDI"), polyphenylpolymethylene polyisocyanates, such as those made by condensation of aniline / formaldehyde and following phosgenation ("crude MDI"), and polyisocyanates that they have carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("polyisocyanates modified "), especially the modified polyisocyanates that derived from 2,4- and 2,6-toluylenediisocyanate or from 4,4'- and / or 2,4'-diphenylmethanediisocyanate.

También se pueden usar prepolímeros de los isocianatos mencionados y compuestos orgánicos con al menos un grupo hidroxilo. Son de mencionar a modo de ejemplo los poliolésteres o poliésteres que presentan uno a cuatro grupos hidroxilo, con pesos moleculares (medios en número) de 60 a 1.400.Prepolymers of the mentioned isocyanates and organic compounds with at least one group hydroxyl The polyesters or polyesters having one to four hydroxyl groups, with weights molecular (number means) from 60 to 1,400.

También se pueden coutilizar parafinas o alcoholes grasos o dimetilpolisiloxanos, así como pigmentos o colorantes, asimismo estabilizadores frente al envejecimiento y a la influencia atmosférica, plastificantes y sustancias de acción fungistática y bacteriostática, así como cargas, tales como sulfato de bario, tierra de diatomeas, negro de carbono o creta lavada. Éstos se añaden al componente de poliol normalmente en cantidades de 0 a 10 partes en peso, preferentemente de 0 a 5 partes en peso.You can also coutilize paraffins or fatty alcohols or dimethylpolysiloxanes, as well as pigments or dyes, also stabilizers against aging and atmospheric influence, plasticizers and substances of action fungistatic and bacteriostatic, as well as fillers, such as sulfate of barium, diatomaceous earth, carbon black or washed crete. These are added to the polyol component normally in amounts of 0 to 10 parts by weight, preferably 0 to 5 parts by weight.

En Vieweg/Höchtlen (ed.). "Kunststoff-Handbuch", volumen VII, Carl Hanser Verlag, Munich 1966, páginas 121 a 205, y G. Oertel (ed.): "Kunststoff-Handbuch", volumen VII, Carl Hanser Verlag, 2ª edición, Munich 1983, se describen otros ejemplos de aditivos tensioactivos y estabilizadores de espuma, así como de reguladores celulares, retardadores de reacción, estabilizadores, sustancias antiinflamables, colorantes y cargas, así como de sustancias de acción fungistática y bacteriostática que se pueden coutilizar dado el caso, así como detalles acerca del modo de uso y de acción de estos aditivos.In Vieweg / Höchtlen (ed.). "Kunststoff-Handbuch", Volume VII, Carl Hanser Verlag, Munich 1966, pages 121 to 205, and G. Oertel (ed.): "Kunststoff-Handbuch", Volume VII, Carl Hanser Verlag, 2nd edition, Munich 1983, describes other examples of surfactant additives and foam stabilizers, as well as cell regulators, reaction retarders, stabilizers, anti-flammable substances, dyes and fillers, as well as substances of fungistatic and bacteriostatic action that can be coutilizar if necessary, as well as details about the mode of use and of action of these additives.

Las espumas de moldeo de poliuretano o de poliisocianurato de acuerdo con la invención presentan una proporción de alvéolos abiertos >85%, preferentemente >90%, medida según DIN ISO 4590-92, y un grado de compactación >3% respecto al volumen mínimo de relleno. El volumen mínimo de relleno de un cuerpo de moldeo es la cantidad de espuma rígida de poliuretano que ha terminado de reaccionar necesaria para llenar justo el molde.Polyurethane or foam molding foams polyisocyanurate according to the invention have a proportion of open alveoli> 85%, preferably> 90%, measured according to DIN ISO 4590-92, and a degree of compaction> 3% with respect to the minimum filling volume. The minimum filling volume of a molding body is the amount of rigid polyurethane foam that has finished reacting necessary to fill just the mold.

El objeto de la invención es también el uso de las espumas rígidas de acuerdo con la invención como capa intermedia para elementos compuestos, como sustratos de relleno para paneles aislantes por vacío y para el espumado de espacios huecos en cámaras frigoríficas, así como en la construcción de contenedores.The object of the invention is also the use of rigid foams according to the invention as intermediate layer for composite elements, such as filler substrates for panels Vacuum and foam insulation of hollow spaces in chambers refrigerators, as well as in the construction of containers.

El procedimiento de acuerdo con la invención se usa preferentemente para el espumado de aparatos frigoríficos y congeladores. También se puede usar en el aislamiento térmico de, por ejemplo, depósitos de agua caliente o tuberías de calor para calefacción. Naturalmente también se pueden fabricar espumas mediante espumación de bloques o según el procedimiento de espumado con cinta transportadora doble conocido en sí (véase "Kunststoffhandbuch", volumen 7: Polyurethane, Carl Hanser Verlag, Munich Viena, 3ª edición 1993, pág. 148).The process according to the invention is preferably used for frothing of refrigerating appliances and freezers It can also be used in thermal insulation of, for example, hot water tanks or heat pipes for heating. Of course you can also make foams by block foaming or according to the foaming process with double conveyor belt known per se (see "Kunststoffhandbuch", volume 7: Polyurethane, Carl Hanser Verlag, Munich Vienna, 3rd edition 1993, p. 148).

Ejemplos Examples

Poliol A:Polyol A:
Poli(óxido de etileno)-poliéter (M_{n} = 300) basado en trimetilolpropanoPoly (ethylene oxide) -polyter (M_ {n} = 300) based on trimethylolpropane

Poliol B:Polyol B:
Polieteréster (M_{n} = 375) basado en anhídrido del ácido ftálico, dietilenglicol y óxido de etilenoPolyether ester (M_ = 375) based on anhydride of phthalic acid, diethylene glycol and ethylene oxide

Poliol C:Polyol C:
Aceite de ricino [empresa Alberding + Boley, Krefeld]Oil of castor [company Alberding + Boley, Krefeld]

Isocianato:Isocyanate:
Polifenilpolimetilenpoliisocianato, contenido en NCO 31,5% en peso (Desmodur® 44V20, Bayer AG)Polyphenylpolimethylene polyisocyanate, contained in NCO 31.5% by weight (Desmodur® 44V20, Bayer AG)

Estabilizador: Stabilizer:
Estabilizador de silicona (Tegostab B 8404, Th. Goldschmidt AG, Essen)Silicone stabilizer (Tegostab B 8404, Th. Goldschmidt AG, Essen)

Emulsionante: Emulsifier:
Sal sulfato sódico de un alcohol de ácido graso etoxilado, al 30% en peso en agua (empresa Servo, NL-Delden)Sodium sulfate salt of a fatty acid alcohol ethoxylated, 30% by weight in water (Servo company, NL-Delden)

Catalizador 1: Catalyst 1:
DimetilciclohexilaminaDimethylcyclohexylamine

Catalizador 2: Catalyst 2:
Acetato de potasio (al 25% en peso en dietilenglicol)Potassium acetate (25% by weight in diethylene glycol)

Las espumaciones se llevaron a cabo en una máquina de alta presión HK 165 de la empresa Hennecke. Se fabricaron en cada caso dos probetas:Foaming was carried out in a HK 165 high pressure machine from Hennecke. They were manufactured in each case two test pieces:

Probeta 1:  Test tube 1:
Bloque de espumado libre de las dimensiones 50 x 50 x 40 cm^{3}Free foam block 50 x 50 dimensions x 40 cm3

Probeta 2: Test tube 2:
Probeta espumada en molde de las dimensiones 9 x 40 x 70 cm^{3}; grado de compresión 8%Foamed specimen in mold of dimensions 9 x 40 x 70 cm3; degree of compression 8%
Ejemplo 1Example 1

(Ejemplo comparativo)(Example comparative)

Se hacen reaccionar 100 partes en peso de una mezcla formada por 92 partes en peso del poliol C, 2,5 partes en peso del catalizador 1, 1 parte en peso del catalizador 2, 2,5 partes en peso de agua y 2 partes en peso de estabilizador con 145 partes en peso de isocianato. La mezcla de poliol es una emulsión blanca.100 parts by weight of one mixture consisting of 92 parts by weight of polyol C, 2.5 parts in catalyst weight 1, 1 part by weight catalyst 2, 2.5 parts by weight of water and 2 parts by weight of stabilizer with 145 parts by weight of isocyanate. The polyol mixture is an emulsion white

Probeta 1:Test tube 1:
Densidad aparente 52 kg/m^{3}; Proporción de alvéolos abiertos (DIN ISO 4590-92): 95%; Tamaño alveolar según imagen de microscopía óptica 100 \mumBulk density 52 kg / m 3;   Proportion of open cells (DIN ISO 4590-92): 95%;    Alveolar size according to optical microscopy image 100 µm

Probeta 2:Test tube 2:
Densidad aparente 75 kg/m^{3}; Proporción de alvéolos abiertos (DIN ISO 4590-92): 93%; Tamaño alveolar según imagen de microscopía óptica 90 \mumBulk density 75 kg / m 3;   Proportion of open cells (DIN ISO 4590-92): 93%;   Alveolar size according to optical microscopy image 90 \ mum
Ejemplo 2Example 2

(Según la invención)(According to invention)

Se hacen reaccionar 100 partes en peso de una mezcla formada por 19,2 partes en peso del poliol A, 19,7 partes en peso del poliol B, 57,7 partes en peso del poliol C, 0,8 partes en peso del catalizador 1, 0,9 partes en peso del catalizador 2, 3,6 partes en peso de emulsionante, 0,9 partes en peso de agua y 1,4 partes en peso de estabilizador con 127 partes en peso de isocianato. La mezcla de polioles es una emulsión blanca.100 parts by weight of one mixture formed by 19.2 parts by weight of polyol A, 19.7 parts in weight of polyol B, 57.7 parts by weight of polyol C, 0.8 parts in catalyst weight 1.0 0.9 parts catalyst weight 3.6 parts by weight of emulsifier, 0.9 parts by weight of water and 1.4 parts by weight of stabilizer with 127 parts by weight of isocyanate The polyol mixture is a white emulsion.

Probeta 1:Test tube 1:
Densidad aparente 46 kg/m^{3}; Proporción de alvéolos abiertos (DIN ISO 4590-92): 98%; Tamaño alveolar según imagen de microscopía óptica 90 \mumBulk density 46 kg / m 3; Proportion of open cells (DIN ISO 4590-92): 98%;   Alveolar size according to optical microscopy image 90 \ mum

Probeta 2:Test tube 2:
Densidad aparente 69 kg/m^{3}; Proporción de alvéolos abiertos (DIN ISO 4590-92): 96%; Tamaño alveolar según imagen de microscopía óptica 80 \mumBulk density 69 kg / m 3;   Proportion of open cells (DIN ISO 4590-92): 96%;   Alveolar size according to optical microscopy image 80 \ mum
Ejemplo 3Example 3

(Ejemplo comparativo)(Example comparative)

Se hacen reaccionar 100 partes en peso de una mezcla formada por 46,3 partes en peso del poliol A, 46,3 partes en peso del poliol B, 2,5 partes en peso del catalizador 1, 1 parte en peso del catalizador 2, 2 partes en peso de agua y 2 partes en peso de estabilizador con 127 partes en peso de isocianato. La mezcla de polioles es una solución transparente.100 parts by weight of one mixture consisting of 46.3 parts by weight of polyol A, 46.3 parts in weight of polyol B, 2.5 parts by weight of catalyst 1, 1 part in catalyst weight 2, 2 parts by weight of water and 2 parts by weight of stabilizer with 127 parts by weight of isocyanate. The mixture of Polyols is a transparent solution.

Probeta 1:Test tube 1:
Densidad aparente 46 kg/m^{3}; Proporción de alvéolos abiertos (DIN ISO 4590-92): 9%; Tamaño alveolar según imagen de microscopía óptica 160 \mumBulk density 46 kg / m 3;   Proportion of open cells (DIN ISO 4590-92): 9%;   Alveolar size according to optical microscopy image 160 \ mum

Probeta 2:Test tube 2:
Densidad aparente 69 kg/m^{3}; Proporción de alvéolos abiertos (DIN ISO 4590-92): 9%; Tamaño alveolar según imagen de microscopía óptica 150 \mumBulk density 69 kg / m 3;   Proportion of open cells (DIN ISO 4590-92): 9%;   Alveolar size according to optical microscopy image 150 \ mum

Los ejemplos muestran que cuando se usan emulsiones de polioles se obtienen espumas rígidas de alvéolos especialmente finos.The examples show that when used emulsions of polyols are obtained rigid foams of alveoli especially fine.

Claims (4)

1. Procedimiento para la fabricación de espumas rígidas de poliuretano y/o de poliisocianurato de alvéolos finos por transformación de1. Procedure for the manufacture of foams rigid polyurethane and / or fine alveoli polyisocyanurate by transformation of A) un poliisocianato con un contenido en NCO del 20 al 48% en peso conA) a polyisocyanate with an NCO content of 20 to 48% by weight with B) un componente de poliol presente en forma de emulsión, que presenta como media al menos dos grupos reactivos frente a isocianato y que contieneB) a polyol component present in the form of emulsion, which has at least two reactive groups on average against isocyanate and containing 1) a) al menos un poliol al menos difuncional inmiscible con agua, con un peso molecular medio en número de 150 a 12.500 g/mol,1) a) at least one at least difunctional polyol immiscible with water, with a number average molecular weight of 150 to 12,500 g / mol, b) al menos un polioléster o polioleteréster con un peso molecular medio en número de 100 a 30.000 g/mol,b) at least one polyol or polyoleter with a number average molecular weight of 100 to 30,000 g / mol, 2) agua,2) water, 3) catalizador,3) catalyst, 4) dado el caso coadyuvantes y aditivos.4) if necessary adjuvants and additives. 2. Procedimiento para la fabricación de espumas rígidas de poliuretano y/o de poliisocianurato de alvéolos finos por transformación de2. Procedure for the manufacture of foams rigid polyurethane and / or fine alveoli polyisocyanurate by transformation of A) un poliisocianato con un contenido en NCO del 20 al 48% en peso conA) a polyisocyanate with an NCO content of 20 to 48% by weight with B) un componente de poliol presente en forma de emulsión, que presenta como media al menos dos grupos reactivos frente a isocianato y que contieneB) a polyol component present in the form of emulsion, which has at least two reactive groups on average against isocyanate and containing 1) a) al menos un polímero inmiscible con agua, con al menos un grupo funcional reactivo frente a isocianato que presenta átomos de hidrógeno y con un peso molecular medio en número de 150 a 12.500 g/mol,1) a) at least one water immiscible polymer, with at least one isocyanate reactive functional group that it has hydrogen atoms and with a number average molecular weight 150 to 12,500 g / mol, b) al menos un polioléter que presenta al menos dos átomos de hidrógeno reactivos frente a isocianato, con un peso molecular medio en número de 150 a 12.500 g/mol,b) at least one polyether having at least two hydrogen atoms reactive to isocyanate, with a weight average molecular number 150 to 12,500 g / mol, c) al menos un polioléster o polioleteréster con un peso molecular medio en número de 100 a 30.000 g/mol,c) at least one polyol or polyoleter with a number average molecular weight of 100 to 30,000 g / mol, 2) agua,2) water, 3) catalizador,3) catalyst, 4) dado el caso coadyuvantes y aditivos.4) if necessary adjuvants and additives. 3. Uso de la espuma fabricada según la reivindicación 1 ó 2 como capa intermedia para elementos compuestos, como sustrato de relleno para paneles aislantes por vacío o como material aislante para aparatos frigoríficos.3. Use of foam manufactured according to claim 1 or 2 as intermediate layer for composite elements, as a filler substrate for vacuum insulating panels or as insulating material for refrigerators. 4. Espuma de moldeo de poliuretano o de poliisocianurato con una proporción de alvéolos abiertos >85%, medida según DIN ISO 4590-92, y un grado de compactación >3% respecto al volumen mínimo de relleno, que se puede obtener según la reivindicación 1 ó 2.4. Polyurethane or foam molding foam polyisocyanurate with a proportion of open alveoli> 85%, measured according to DIN ISO 4590-92, and a degree of compaction> 3% with respect to the minimum filling volume, which is can be obtained according to claim 1 or 2.
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Families Citing this family (78)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10060817A1 (en) * 2000-12-07 2002-06-20 Henkel Kgaa Stone composite panels for insulation
US6833431B2 (en) * 2001-05-02 2004-12-21 Bayer Aktiengesellschaft Double-metal cyanide catalysts for preparing polyether polyols
DE102004062540A1 (en) * 2004-12-24 2006-07-06 Bayer Materialscience Ag Rigid polyurethane foams, a process for their preparation and their use
ATE432304T1 (en) * 2006-01-27 2009-06-15 Basf Se METHOD FOR PRODUCING OPEN-CELL VISCOELASTIC SOFT POLYURETHANE FOAM
CN101631810B (en) 2006-12-29 2013-07-24 江森自控科技公司 Polyurethane foam formulation, products and methods
JP2009040916A (en) * 2007-08-09 2009-02-26 Nippon Polyurethane Ind Co Ltd Composition for forming water-expanded rigid polyisocyanurate foam, method for production of water-expanded rigid polyisocyanurate foam using the composition, and water-expanded rigid polyisocyanurate foam produced by the method
EP2072548B1 (en) * 2007-12-19 2017-02-22 Basf Se Method for manufacturing rigid foams containing urethane and isocyanurate groups
DE102008000243A1 (en) 2008-02-06 2009-08-13 Evonik Goldschmidt Gmbh Novel compatibilizers to improve the shelf life of polyol blends
DE102008000255A1 (en) 2008-02-08 2009-08-20 Evonik Goldschmidt Gmbh siloxane
DE102009001595A1 (en) 2009-03-17 2010-09-23 Evonik Goldschmidt Gmbh Compatibilizer for improving the storage stability of polyol blends
WO2012007418A1 (en) 2010-07-13 2012-01-19 Bayer Materialscience Ag Lightly modified prepolymers and uses thereof
DE102010060390A1 (en) * 2010-11-05 2012-05-10 Bayer Materialscience Aktiengesellschaft Emulsion-shaped reaction mixture and process for producing polyurethane foams from such a reaction mixture
DE102010063241A1 (en) 2010-12-16 2012-06-21 Evonik Goldschmidt Gmbh Silicone stabilizers for rigid polyurethane or polyisocyanurate foams
DE102011007479A1 (en) 2011-04-15 2012-10-18 Evonik Goldschmidt Gmbh Composition containing specific amides and organomodified siloxanes, suitable for the production of polyurethane foams
DE102011007468A1 (en) 2011-04-15 2012-10-18 Evonik Goldschmidt Gmbh Composition containing specific carbamate-type compounds suitable for the preparation of polyurethane foams
US20130030073A1 (en) * 2011-07-26 2013-01-31 Bayer Materialscience Llc Amine-initiated polyols from renewable resources and processes for their production and use
DE102011109541A1 (en) 2011-08-03 2013-02-07 Evonik Goldschmidt Gmbh Use of polysiloxanes containing branched polyether radicals for the production of polyurethane foams
ES2627929T3 (en) * 2011-08-23 2017-08-01 Basf Se Use of microemulsions and procedure for the preparation of sponge material
DE102013201829A1 (en) 2013-02-05 2014-08-07 Evonik Industries Ag Amines suitable for use in the production of polyurethanes
CN105492486B (en) * 2013-08-13 2019-03-01 科思创德国股份有限公司 Polyurethane foam and application thereof
DE102013217395A1 (en) 2013-09-02 2015-03-05 Evonik Industries Ag Use of mixtures of organofunctionally modified polysiloxanes with amides in the production of flexible polyurethane foams
EP2886591A1 (en) 2013-12-19 2015-06-24 Evonik Industries AG Composition, suitable for the production of polyurethane foams, containing at least one nucleating agent
DE102013226575B4 (en) 2013-12-19 2021-06-24 Evonik Operations Gmbh Composition suitable for the production of polyurethane foams, containing at least one unsaturated fluorocarbon or unsaturated fluorocarbon as blowing agent, polyurethane foams, processes for their production and their use
DE102014215380B4 (en) 2014-08-05 2022-04-28 Evonik Operations Gmbh Nitrogen-containing compounds suitable for use in the manufacture of polyurethanes
DE102014215383B4 (en) 2014-08-05 2020-06-10 Evonik Operations Gmbh Nitrogen containing compounds suitable for use in the manufacture of polyurethanes
DE102014215384A1 (en) 2014-08-05 2016-02-11 Evonik Degussa Gmbh Nitrogen containing compounds suitable for use in the production of polyurethanes
DE102014215387B4 (en) 2014-08-05 2020-06-10 Evonik Operations Gmbh Nitrogen containing compounds suitable for use in the manufacture of polyurethanes
DE102014215388A1 (en) 2014-08-05 2016-02-11 Evonik Degussa Gmbh Nitrogen containing compounds suitable for use in the production of polyurethanes
DE102014215381B4 (en) 2014-08-05 2020-06-10 Evonik Operations Gmbh Nitrogen containing compounds suitable for use in the manufacture of polyurethanes
DE102014215382A1 (en) 2014-08-05 2016-02-11 Evonik Degussa Gmbh Nitrogen containing compounds suitable for use in the production of polyurethanes
ES2845608T3 (en) 2015-03-03 2021-07-27 Evonik Operations Gmbh Production of porous polyurethane layers
EP3078696A1 (en) 2015-04-08 2016-10-12 Evonik Degussa GmbH Production of low-emission polyurethanes
ES2793850T3 (en) 2015-07-07 2020-11-17 Evonik Degussa Gmbh Production of polyurethane foam
EP3176206A1 (en) 2015-12-01 2017-06-07 Evonik Degussa GmbH Method for the preparation of fine cell foams using a cell aging inhibitor
EP3205678A1 (en) 2016-02-10 2017-08-16 Evonik Degussa GmbH Aging-resistant and low-emission mattresses and/or cushions
EP3459984A1 (en) 2017-09-25 2019-03-27 Evonik Degussa GmbH Preparation of polyurethane foam
EP3720892B1 (en) * 2017-12-05 2022-01-19 Basf Se Method for producing urethane groups and open-cell solid foams containing isocyanurate groups
WO2020081416A1 (en) 2018-10-15 2020-04-23 Dow Global Technologies Llc Formulated polyol compositions
ES2898877T3 (en) 2019-01-07 2022-03-09 Evonik Operations Gmbh Production of hard polyurethane foam
WO2020144003A1 (en) 2019-01-07 2020-07-16 Evonik Operations Gmbh Production of rigid polyurethane foam
EP3744745A1 (en) 2019-05-28 2020-12-02 Evonik Operations GmbH Production of pu foams
US20210015269A1 (en) 2019-07-19 2021-01-21 Evonik Operations Gmbh Shaped pu foam articles
EP4004079A1 (en) 2019-07-24 2022-06-01 Evonik Operations GmbH Preparation of polyurethane systems
EP3805285A1 (en) 2019-10-08 2021-04-14 Evonik Operations GmbH Preparation of polyurethane rigid foam
EP3819323A1 (en) 2019-11-07 2021-05-12 Evonik Operations GmbH Compression set
EP3865527A1 (en) 2020-02-14 2021-08-18 Evonik Operations GmbH Production of pu foams
DE102020202057A1 (en) 2020-02-19 2021-08-19 Evonik Operations Gmbh Polyurethane insulation foams and their manufacture
EP3919539A1 (en) 2020-06-04 2021-12-08 Evonik Operations GmbH Preparation of polyurethane foam
EP3940012A1 (en) 2020-07-16 2022-01-19 Evonik Operations GmbH Nitrogen-free and low-nitrogen crosslinking additives for cold block soft foam with improved compression and ageing properties
US20220056231A1 (en) 2020-08-20 2022-02-24 Evonik Operations Gmbh Production of polyurethane foam
US20220106432A1 (en) 2020-10-07 2022-04-07 Evonik Operations Gmbh Shaped flexible pu foam articles
WO2022122360A1 (en) 2020-12-08 2022-06-16 Evonik Operations Gmbh Production of polyurethane foam
KR20230154044A (en) 2021-03-02 2023-11-07 에보니크 오퍼레이션즈 게엠베하 Preparation of polyurethane foam
WO2022218657A1 (en) 2021-04-14 2022-10-20 Evonik Operations Gmbh Production of hard polyurethane or polyisocyanurate foam
CN117529512A (en) 2021-06-17 2024-02-06 赢创运营有限公司 Molded flexible polyurethane foam article
EP4363480A1 (en) 2021-07-01 2024-05-08 Evonik Operations GmbH Production of hard polyurethane or polyisocyanurate foam
CN117597373A (en) 2021-07-02 2024-02-23 赢创运营有限公司 Production of PU foam
CN117580885A (en) 2021-07-02 2024-02-20 赢创运营有限公司 PU foam production using recycled polyol
EP4363472A1 (en) 2021-07-02 2024-05-08 Evonik Operations GmbH Production of pu foams using recycled polyols
EP4363478A1 (en) 2021-07-02 2024-05-08 Evonik Operations GmbH Production of pu foams using recycled polyols
WO2023275033A1 (en) 2021-07-02 2023-01-05 Evonik Operations Gmbh Production of pu foams using recycled polyols
CN117642446A (en) 2021-07-02 2024-03-01 赢创运营有限公司 Recovery of di-and/or polyisocyanates from PU depolymerization process
WO2023161253A1 (en) 2022-02-22 2023-08-31 Evonik Operations Gmbh Use of recycled polyol from amine-based hydrolysis process to produce pu foam
EP4257326A1 (en) 2022-04-08 2023-10-11 Evonik Operations GmbH Optical determination of a control signal in response to detection of macroscopic polyurethane foam defects
EP4257327A1 (en) 2022-04-08 2023-10-11 Evonik Operations GmbH Optical determination of a control signal for slabstock polyurethane foam production
EP4257325A1 (en) 2022-04-08 2023-10-11 Evonik Operations GmbH Optical prediction of polyurethane foam parameters
EP4257324A1 (en) 2022-04-08 2023-10-11 Evonik Operations GmbH System and method for automatically setting parameters for foam production
EP4257323A1 (en) 2022-04-08 2023-10-11 Evonik Operations GmbH System and method for determining parameters for foam production
WO2023222400A1 (en) 2022-05-17 2023-11-23 Evonik Operations Gmbh Production of polyurethane foam
EP4282892A1 (en) 2022-05-25 2023-11-29 Evonik Operations GmbH Preparation of polyurethane foam using ionic liquids based catalysts
EP4282890A1 (en) 2022-05-25 2023-11-29 Evonik Operations GmbH Preparation of polyurethane foam using ionic liquids
WO2023237418A1 (en) 2022-06-08 2023-12-14 Evonik Operations Gmbh Production of flame-retardant polyurethane foam
WO2023237420A1 (en) 2022-06-08 2023-12-14 Evonik Operations Gmbh Polyether-siloxane block copolymers for producing polyurethane foams
EP4299656A1 (en) 2022-07-01 2024-01-03 Evonik Operations GmbH Preparation of propoxylated benzenedicarboxylic acid amides and corresponding polyurethane foam
WO2024046954A1 (en) 2022-08-31 2024-03-07 Evonik Operations Gmbh Production of polyurethane foam
WO2024068268A1 (en) 2022-09-28 2024-04-04 Evonik Operations Gmbh Method for producing sioc-linked, linear polydialkylsiloxane-polyether block copolymers and the use thereof
EP4372036A1 (en) 2022-11-15 2024-05-22 Evonik Operations GmbH Depolymerization of polyisocyanurate with organic amine bases
EP4372024A1 (en) 2022-11-15 2024-05-22 Evonik Operations GmbH New method for recycling of polyisocyanurates

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3621039A1 (en) * 1986-06-24 1988-01-07 Bayer Ag METHOD FOR PRODUCING OLIGOESTERS HAVING HYDROXYL GROUPS AND THE USE THEREOF
JPH02180916A (en) * 1989-01-06 1990-07-13 M D Kasei Kk Production of rigid polyurethane foam
JPH03195718A (en) * 1989-12-25 1991-08-27 Mitsui Toatsu Chem Inc Production of rigid urethane foam
DE4303556C1 (en) * 1993-02-08 1994-10-27 Bayer Ag Hard polyurethanes or polyurethane foams
ATE169039T1 (en) * 1993-02-10 1998-08-15 Bayer Ag METHOD FOR PRODUCING ISOCYANATE-BASED FOAM
GB9314556D0 (en) * 1993-07-14 1993-08-25 Ici Plc Rigid polyurethane foams
EP0672697A1 (en) * 1994-03-17 1995-09-20 Bayer Ag Process for the preparation of rigid foams having urethane, urea and biuret groups and their use
JP3425816B2 (en) * 1995-01-19 2003-07-14 三井化学株式会社 Rigid polyurethane foam
DE19634392A1 (en) * 1996-08-26 1998-03-05 Bayer Ag Foaming polyurethane formulations with good flow behavior and a process for producing foamed polyurethane moldings
GB2324798B (en) * 1997-05-01 1999-08-18 Ici Plc Open celled cellular polyurethane products
DE19742010A1 (en) * 1997-09-24 1999-03-25 Basf Ag Storage-stable emulsions for the production of fine-celled rigid foams based on isocyanate

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